Substitute for celluloid and method of making same.



: TIT'UTE FOR CELLULOID AND METHOD IVIAKING SAME.

eretic.

No Drawing.

To all whom it may concern:

Be it known that T, HENRY DREYFUS, doctor of philosophy, chemist, a citizen of the Republic of Switzerland, residing at Basel, 5 Switzerland, (whose post-oflice address is 69 Schiitzenmattstrasse, Basel, Switzerland,) have invented a Substitute for. Celluloid and Method of Making Same, of which the fo1- lowing description is a specification.

Heretofore l[ have applied for patents in the following countries: In France on the th July 1911 in Germany the 17th July products have been found which are capable of replacing camphor with great advantage. These products can be employed both with cellulose acetates or cellulose esters of other fatty acids; they can be used with the 1 same advantage with mixtures of nitrocellulose and acetate of cellulose or other cellulosic esters. If cellulose acetates or other analogous cellulosic esters are exclusively employed in combination with these new camphor substitutes, the resulting products are comparatively non-infiammable The solvents or camphorsubstitutes employed in the present invention are the fol lowing:

(A) The ethers of phenols, creso'ls, and their homologues, for example: anisol,

(B) The ethers of naphthols, such as those of alphaor beta-naphthol, such as methyl ea or ethyl ethers, or homologues thereof.

(C) Ethers of poly-hydric phenols, such I as those of resorcinol, pyrocatechol, such as the methyl or ethyl ethers, or homologues thereof, for example: veratrol,

CH OC H -OCH pyrocatechol diethyl ether C H -O C H O C H M (D) Ethers of higher aromatic alcohols phenetol Specification of Letters Patent.

Patented May 2, 1916.

Application filed October 2, 1911. Serial No. 652,445.

such as those of benzyl alcohol, for example benzyl methyl ether safrol,

isosafrol,

- (E) Other etherified derivatives such as (F) Ethers of phenols (or the liire as i c u owai (G) Mixtures of two or more of the materlals referred to in the above paragraphs A to F. With these new products it is possible, according to desire or requirement, to manufacture hard or soft materlals in any gradation, employing them alone or adding oils such as castor oil or any other additions or filling substances. These products are indifierent toward organic or inorganic coloring matters and the usual filling substances, and they mix with these latter in a manner analogous to that practised with ordinary celluloid made with camphor.

These substances are characterized by their great stability, being at least as stable as camphor. Camphor, when used in conjunction with nitrocellulose exerts no other action than its solvent action. It does not decompose, form acids, etc., and accordingly does not have any bad effects on the nitrocellulose, and in the same way neither'do the substances which I use in my process, and the substances 1 use have the advantages over camphor that they do not burn, andare not as volatile as camphor. These products are also very stable, that is, at least as stable as camphor, and. many are more stable. These products may be, for the most part, prepared in a comparatively pure state at the cost much less than that of camphor.

The products or series of products may be employed alone or in mixtures of two or more together, and preferably in presence of alcohol or substitutes thereof or of mixtures of such substitutes with or without alcohol. These products may also beemployed simultaneously and in combination with those ployed are suitably chosen,

indicated in my copending application, 652,444, filed concurrently herewith, that is to say with the chlorinated derivatives of ethylene and ethane, such as dichlorethylene, pentachlorethane, tetrachlorethane, trichlorethylene, or their mixtures.

f the proportions of the quantities emthe resulting materials can be worked up on the usual celluloid machines, for example rollers, presses,-

etc., as well as cast directly to make objects of any shape and kind according to particular desires or requirements. These products may also be employed alone or in combination with the chlorinated derivatives of ethylene or ethane, for the manufacture of solutions of any nature and for any other use whatever, such as for the manufacture of varnishes, lacquers, films, artificial silk, artificial horse hair, coatings of all kinds, etc., and. for other employments. It has moreover" been found that these products can also be employed in combination with bodies such as ethylene chlorid, methylene chlorid, ethylidene chlorid, methylal and its .homologues, either singly or mixed, and also in combination with the chlorinated derivatives of ethylene and ethane'and particularly in presence of alcohol or substitutes therefor orof mixtures of such substitutes with or without alcohol. The products dichlorethylene,

trichlorethylene, ethylene chlorid, methylene chlorid, ethylidene chlorid, etc., may be employed alone or' in mixtures of two or more together, and in presence of alcohol or alcohol substitutes or of mixtures of such substitutes with or without-alcohol. The employment of these latter products in many cases presents an advantage over products having a higher boilabove mentioned, such for example as ethyl- L ene chlorid, methylene chlorid, ethylidene chlorid, methylal and its homologues, at the same time represent a series of new solvents for the acetates of cellulose; thus for example ethylidene chlorid represents a very advantageous substitute for chloroform and tetrachlorethane, and like these latter dissolvesthe acetates or other cellulosic esters that are soluble in chloroform, while the cellulosic esters that are diflicultly soluble or. insoluble in' chloroform are likewise insoluble in this product, but certain ,of said esing point, such as tetrachlorethane, anisol, etc., or their mixtures, and especially so in cases where it is desired to obtain easy and rapid evaporation. Thus one preferably employs for example a quarter to half a kilo or more of these products to a kilo of acetylated cellulose, according to the particular employment in view, and half a liter to a liter or more of alcohol. The alcohol may be replaced by its substitutes or as before mentioned by mixtures of such substitutes with or without alcohol. Some of these products may be employed without alcohol or alcohol substitutes.

The procedure for the preparation of solutions with solvents of low boiling points, such as the alcohols and chlorinated compounds above referred to, together with the herein described camphor. substitutes, being substances which act as solvents of nitrocellulose, or cellulose acetates, is illustrated in the following examples.

Example I: 200. parts of the cellulose acetate herein above referred to, which is inters give concentrated and viscous solu-- tions therein on addition of alcohol. The other chlorinated derivatives such as methylene chlorid, etc., behave in the same way.

Now I have found in the course of the present invention that especially the acetates of cellulose that are readily soluble in mixtures of alcohol and tetrachlorethane, are capableon heating with a mixture of trichlorethylene and alcohol, of giving viscous andconcentrated solutions which congeal on cooling; it is advantageous to employ mixtures of alcohol and trichlorethylene in proportions of, equal volumes; if one adds to these solutions other solvents 'such for example as dichlorethylene, pentachlorethane, manol (methyl acetanilid' tetrachlorethane, anisol,. dichlorbenzenes, etc., the solutions remain liquid even on cooling.

. Thesolvents of low boiling point, such as soluble or difiicultly soluble in chloroform but readily soluble in'a mixture of chloroform and alcohol are dissolved by adding in a mixture of 200 parts of alcohol and 200 parts of dichlorethane or dichlormethane, together with any one or more of the camphor substitutes above referred to. The solution thus obtained is employed for the production of films or coatings or the like.

Example II: 100 parts of cellulose acetate, particularly the cellulose acetate above referred to, are dissolved in a heated mixture of equal volumes of alcohol and trichlorethylene, together with any one or more of the above mentioned camphor substitutes.

The solution in this example remains liquid when cold.

In the above examples one or more of the camphor substitutes mentioned. can be employed, together with any of the above men tioned solvents, in which the particular cellulose acetate employed, is soluble. Some of these camphor substitutes possess alone or mixed two or more together a dissolving power for 'these acetates of cellulose or cellulosic esters, which are insoluble in chloroform, but soluble in chloroform-alcohol. Some of these products or mixtures of two or more also dissolve those acetates of cellulose which are soluble in chloroform. The non-inflammable celluloid masses thus iterate 7 lat obtained, '5. 6., solutions of cellulosic esters serve industrially as substitutes for cellulold and for the manufacture of objects, articles, products. etc., of every nature, such as films, varnishes, coatings, artificial silk, artificial leather, etc.

What I claim is a 1. A process of making a celluloid substitute which comprises'dissolving a cellulose ester-of a fatty acid in a solvent including an etherified phenol.

2. A process of making a celluloid substitute which comprises dissolving a cellulose ester of a fatty acid in a solvent including alcohol and an etherified phenol.

3. A process of making solutions for the manufacture of celluloid substitutes which comprises dissolving a cellulose acetate in a solventincluding an etherified phenol.

l. A process for making solutions for the manufacture of celluloid substitutes which comprises dissolving a cellulose ester of a fatty acid in a solvent including alcohol,

chlorin derivatives of fatty hydrocarbons and an etherified phenol.

5. A celluloid substitute including a cellulose ester of a fatty acid and a solvent in cluding an etherified phenol.

6. A celluloid substitute including a cellulose ester of a fatty acid and nitrocellulose and a solvent including an etherified phenol.

7. A celluloid substitute including a cellulose acetate not readily soluble in tetrachlor ethane. but readily soluble in alcohol-tetrachlorethane mixture, and a solvent including an etherified phenol.

In testimony whereof l have hereunto set my hand in the presence of two subscribing witnesses.

Paris, dated this 20th day of September, 1911.

'DR. HENRY DREYFUS.

ll itnesses H. C. COKE. CAMILLE DREYFUS. 

